Anions of 1,3,5-Benzenetricarboxylic and Heptanedioic Acids Serving as Bridges between Dimolybdenum(V) Metal–Metal Bonded Units: Preparation and Structural Characterization of Dinuclear and Tetranuclear Complexes

✍ Scribed by Barbara Modec; Jurij V. Brenčič

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 187 KB
• Volume: 2005
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200500469

✦ Synopsis

Abstract

(PyH)~5~[MoOCl~4~(H~2~O)]~3~Cl~2~ and (PyH)[MoOBr~4~] reacted with the anions of 1,3,5‐benzenetricarboxylic acid (btcH~3~) and heptanedioic acid (hdaH~2~) to afford a series of novel carboxylato complexes based on the {Mo~2~O~4~}^2+^ structural core: (PyH)~4~[Mo~2~O~4~Cl~4~(μ~2~‐btcH~2~)]Cl (1), (PyH)~4~[Mo~2~O~4~Br~4~(μ~2~‐btcH~2~)]Br (2), [(Mo~2~O~4~Py~3~)~2~(μ~3~‐btcH)~2~]·6Py (3), (PyH)~6~[(Mo~2~O~4~Cl~4~)~2~(μ~4~‐hda)]·2CH~3~CN (4), and (PyH)~10~[(Mo~2~O~4~Cl~4~)~2~(μ~4~‐hda)][MoOCl~5~]Cl~2~ (5) {Py = pyridine, C~5~H~5~N; PyH^+^ = pyridinium cation, C~5~H~5~NH^+^; btcH~2~^–^ = (HOOC)~2~C~6~H~3~COO^–^; btcH^2–^ = (HOOC)C~6~H~3~(COO)~2~^2–^ and hda^2–^ = ^–^OOC(CH~2~)~5~COO^–^}. A pair of isostructral compounds 1 and 2 contains dinuclear anions [Mo~2~O~4~X~4~(μ~2~‐btcH~2~)]^3–^ (X = Cl, Br) in which the btcH~2~^–^ ligand is bonded to the {Mo~2~O~4~}^2+^ core via one carboxylate group in a syn‐syn bidentate bridging manner. In 3, two btcH^2–^ ligands link two {Mo~2~O~4~}^2+^ cores into a loop‐like structure. Each btcH^2–^ ligand is coordinated via two carboxylate groups, with one in the syn‐syn bidentate bridging manner and with another in a monodentate manner. The linkage of two dinuclear subunits was also realized in [(Mo~2~O~4~Cl~4~)~2~(μ~4~‐hda)]^6–^, the anion in 4 and 5, where both carboxylate groups of the hda^2–^ ligand bind in the syn‐syn bidentate‐bridging manner to {Mo~2~O~4~}^2+^ cores. The title compounds were characterized by X‐ray crystallography and infrared spectroscopy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)